Patent GB-2342649-A (GB)
Title: Heterocyclic Alkoxyamines as Regulators in controlled Radical Polymerization processes
Inventor: NESVADBA PETER
IPC: C08F2/00
Filed: 1999-10-06
Abstract: A polymerizable composition, comprising <SL> <LI>a) at least one ethylenically unsaturated monomer or oligomer, and <LI>b) a compound of formula (Ia) or (Ib) <EMI ID=1.1 HE=35 WI=79 LX=698 LY=549 TI=CF> </SL> (Ib), wherein<BR> R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB> and R<SB>4</SB> independently of each other are C<SB>1</SB>-C<SB>18</SB>alkyl, C<SB>3</SB>-C<SB>18</SB>alkenyl, C<SB>3</SB>-C<SB>18</SB>alkinyl, C<SB>1</SB>-C<SB>18</SB>alkyl, C<SB>3</SB>-C<SB>18</SB>alkenyl, C<SB>3</SB>-C<SB>18</SB>alkinyl which are substituted by OH, halogen or a group -O-C(O)-R<SB>5</SB>, C<SB>2</SB>-C<SB>18</SB>alkyl which is interrupted by at least one O atom and/or NR<SB>5</SB> group, C<SB>3</SB>-C<SB>12</SB> cycloalkyl or C<SB>6</SB>-C<SB>10</SB>aryl or R<SB>1</SB> and R<SB>2</SB> and/or R<SB>3</SB> and R<SB>4</SB> together with the linking carbon atom form a C<SB>3</SB>-C<SB>12</SB>cycloalkyl radical;<BR> with the proviso that if Q in formula (Ia) is a direct bond, -CH<SB>2</SB>- or CO, at least one of R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB> or R<SB>4</SB> is different from methyl;<BR> R<SB>5</SB>, R<SB>6</SB> and R<SB>7</SB> independently are hydrogen, C<SB>1</SB>-C<SB>18</SB>alkyl or C<SB>6</SB>-C<SB>10</SB>aryl;<BR> X represents a group having at least one carbon atom and is such that the free radical X  Ò    derived from X is capable of initiating polymerization of ethylenically unsaturated monomers; Z<SB>1</SB> is O or NR<SB>8</SB>;<BR> R<SB>8</SB> is hydrogen, OH, C<SB>1</SB>-C<SB>18</SB>alkyl, C<SB>3</SB>-C<SB>18</SB>alkenyl, C<SB>3</SB>-C<SB>18</SB>alkinyl, C<SB>1</SB>-C<SB>18</SB>alkyl, C<SB>3</SB>-C<SB>18</SB>alkenyl, C<SB>3</SB>-C<SB>18</SB> alkinyl which are substituted by one or more OH, halogen or a group -O-C(O)-R<SB>5</SB>, C<SB>2</SB>-C<SB>18</SB> alkyl which is interrupted by at least one O atom and/or NR<SB>5</SB> group, C<SB>3</SB>-C<SB>12</SB>cycloalkyl or C<SB>6</SB>-C<SB>10</SB>aryl, C<SB>7</SB>-C<SB>9</SB>phenylalkyl, C<SB>5</SB>-C<SB>10</SB>heteroaryl, -C(O)-C<SB>1</SB>-C<SB>18</SB>alkyl, -O-C<SB>1</SB>-C<SB>18</SB>alkyl or -COOC<SB>1</SB>-C<SB>18</SB> alkyl;<BR> Q is a direct bond or a divalent radical CR<SB>9</SB>R<SB>10</SB>, CR<SB>9</SB>R<SB>10</SB>-CR<SB>11</SB>R<SB>12</SB>, CR<SB>9</SB>R<SB>10</SB>CR<SB>11</SB>R<SB>12</SB>CR<SB>13</SB>R<SB>14</SB>, C(O) or CR<SB>9</SB>R<SB>10</SB>C(O), wherein R<SB>9</SB>, R<SB>10</SB>, R<SB>11</SB>, R<SB>12</SB>, R<SB>13</SB> and R<SB>14</SB> are independently hydrogen, phenyl or C<SB>1</SB>-C<SB>18</SB>alkyl;<BR> with the proviso that the compounds (A) and (B) are excluded <EMI ID=1.2 HE=22 WI=107 LX=610 LY=1981 TI=CF> Further aspects of the invention are a process for polymerizing ethylenically unsaturated monomers, and the use of heterocyclic alkoxyamine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention. Still further subjects of the invention are novel amine precursors and a novel process for manufacturing 5-ring heterocyclic amines.